Pore network modeling of cathode catalyst layer of proton exchange membrane fuel cell

In this paper, a pore network model is developed to investigate the coupled transport and reaction processes in the cathode catalyst layer (CCL) of proton exchange membrane fuel cell (PEMFC). The developed model is validated by comparing the predicted polarization curve with the experimental data, and the parametric studies are carried out to elucidate the effects of CCL design parameters. With the decrease of the CCL thickness and the Nafion content, the cell voltage reduces at the low current density but increases when the current density is higher. The cell performance is also improved by increasing the proton conductivity of the Nafion film in the CCL. As compared to the CCL of uniformly distributed Nafion, the CCL with the Nafion volume decreasing along the thickness direction exhibits better performance at the high current density.     

Performance prediction of PEM fuel cell cathode catalyst layer using agglomerate model

Computation of Proton Exchange Membrane (PEM) fuel cell's cathode Catalyst Layer (CL) is performed using agglomerate models in this paper, and the results are compared with homogenous one. Following our earlier homogenous model for cathode CL (see Khajeh-Hosseini et al., 2010), the focus of the present study is on agglomerate model. In this study, the derivation of agglomerate model is performed in such a way that in the simplified case when agglomerate sizes shrink to zero, the homogeneous model condition is retrieved. Validations versus two sets of experimental data are performed. For example, in one of the validation cases, Case (II), it is observed that in I_tot = 3000 [A m⁻²] the homogeneous model overestimates the performance by 80%. But the agglomerate model agrees well with the validating test cases. A set of parametric studies are performed using the agglomerate model, in which the influences of some CL structural- and cell operating-parameters are studied. A sensitivity study on the cell performance is performed to rank the influence of the parameters, with rank 1 for the most influential parameter. It is observed the agglomerate sizes possess rank 1. These results give useful guidelines for manufactures of PEMFC catalyst layers.     

Influence of catalyst layer polybenzimidazole molecular weight on the polybenzimidazole-based proton exchange membrane fuel cell performance

The catalyst layer (CL) of a polybenzimidazole (PBI) membrane electrode assembly (MEA) consists of Pt–C (Pt on a carbon support), PBI, and H₃PO₄. Two series of catalyst ink solutions each containing Pt–C, N,N′-dimethyl acetamide, and PBIs comprising four different molecular weights (MWs) (i.e., M_w = 1.1 × 10⁴, 4.4 × 10⁴, 9.0 × 10⁴, and 17.4 × 10⁴ g mol⁻¹) are used to fabricate CLs. One catalyst ink solution series is mixed with LiCl, while the other solution series lacks LiCl. We demonstrate that the CL prepared using a lower MW PBI has a higher electrochemical surface area, lower charge transfer resistance, and higher fuel cell performance. The addition of LiCl enhances the dispersion of the high MW PBIs in the catalyst ink solution and acts as a foaming agent in CL, thus improving fuel cell performance. However, LiCl exerts small influence on the fuel cell performance of the MEAs fabricated using low MW PBIs.     

Study of cell voltage uniformity of proton exchange membrane fuel cell stack with an optimized artificial neural network model

The cell voltage uniformity of the proton exchange membrane fuel cell stack, which may consist of tens or hundreds of cells in series, plays a significant role in the stack's lifetime and performance. But it is challenging to predict the multi-cell voltages and the uniformity with a physics-based model due to complex stack geometry and huge computation efforts. In this work, we develop an artificial neural network model to estimate the steady-state cell voltage distributions of a 60 kW 140-cell stack. The optimized and well-trained model can efficiently reproduce the 140-cell voltages at different operating conditions with the error of less than 2 mV. The increased cathode gas pressure improves the cell voltage consistency and stack performance, while the voltage uniformity worsens with ascending load current. The efficient model prediction of cell voltages is beneficial for accurate evaluation of fuel cell performance, health state, and reliability.     

Prediction of the effective conductivity of Nafion in the catalyst layer of a proton exchange membrane fuel cell

In a previous study, a simple acid catalyzed reaction (esterification) was found to predict excellently conductivity of a membrane contaminated with NH₄⁺ or Na⁺. Since measurement of the conductivity of Nafion in a catalyst layer is problematic, being able to predict this conductivity for various formulations and fuel cell conditions would be advantageous. In this study, the same methodology as before was used to examine the proton availabilities of supported Nafion (Nafion on carbon and on Pt/C), as exists in the catalyst layer used in a PEMFC, during impurity exposure (e.g., NH₃) as a means for prediction of its conductivity. It was found that the effect of NH₃ exposure on the proton composition (yH+) of supported Nafion was similar to that of N-211 under the same conditions. Determined values of yH+ were then used to estimate the effective conductivity of an ammonium-poisoned cathode layer using the correlation developed and the agglomerate model. The predicted conductivities were matched with the results available in the literature. This technique would be useful for the optimization of catalyst design and for fuel cell simulation, since it provides many benefits over conventional performance test procedures.     

Characteristics of proton exchange membrane fuel cells cold start with silica in cathode catalyst layers

In this study, a novel strategy is reported to improve the cold start performance of proton exchange membrane (PEM) fuel cells at subzero temperatures. Hydrophilic nano-oxide such as SiO₂ is added into the catalyst layer (CL) of the cathode to increase its water storing capacity. To investigate the effect of nanosized SiO₂ addition, the catalyst coated membranes (CCMs) with 5 wt.% and without nanosized SiO₂ are fabricated. Although at normal operation conditions the cell performance with nanosized SiO₂ was not so good as that without SiO₂, cold start experiments at −8 °C showed that the former could start and run even at 100 mA cm⁻² for about 25 min and latter failed very shortly. Even at −10 °C, the addition of SiO₂ dramatically increased the running time before the cell voltage dropped to zero. These results further experimentally proved the cold start process was strongly related with the cathode water storage capacity. Also, the performance degradation during 8 cold start cycles was evaluated through polarization curves, cyclic voltammetry (CV) and electrochemical impedance spetra (EIS). Compared with the cell without SiO₂ addition, the cell with 5 wt.% SiO₂ indicated no obvious degradation on cell performance, electrochemical active surface area and charge transfer resistance after experiencing cold start cycles at −8 °C.     

Dodecylamine-modified carbon supports for cathode in proton exchange membrane fuel cells

In this investigation, hydrophobic dodecylamine-modified carbon supports are prepared for proton exchange membrane fuel cells by organic synthesis. Well-dispersed Pt-Ru nanoparticles, with a narrow size distribution, are then deposited on the dodecylamine-modified carbon supports by methanol reduction to serve as cathodic catalysts. These dodecylamine-modified catalysts are separately mixed with either a commercial catalyst or unmodified catalyst to provide hydrophobic channels to convey the reaction gas to the active sites in the catalyst layer. The best cathode composite catalyst, containing 20-40 wt% of modified-catalyst, gives approximate 30% increase in the maximum power density, comparing to E-TEK catalyst (125 mW cm⁻²). The increase in the maximum power density is attributed to higher activity and lower resistance. This result is discussed in the context of AC-impedance and proton conductivity analysis.     

Optimization of cathode microporous layer materials for proton exchange membrane fuel cell

The microporous layer (MPL) of diffusion medium has an important impact on the water management ability of proton exchange membrane fuel cells. In this study, six kinds of carbon black were used to prepare the cathode MPL. The thickness, conductivity, pore structure, hydrophobicity, and surface microstructure of MPL were characterized. The single cell was prepared and electrochemical tests were performed. The results showed that the single cell prepared by Acetylene black (ACET) and Vulcan XC-72R has a considerable power generation performance. In addition, polyvinylidene fluoride hexafluoropropylene copolymer P(VDF-HFP) was used to replace Polytetrafluoroethylene (PTFE) as hydrophobic binder. MPL with different P(VDF-HFP) contents were prepared, and the single cell performance was investigated. The results showed that all the single cells prepared by P(VDF-HFP) were worse than that of PTFE. This study provides an important reference for further improving the performance of fuel cells from the perspective of material optimization with MPL.     

Computational modeling and experimental verification of cathode catalyst layer on PEM fuel cells

Fuel cell systems are environmentally friendly energy converters that directly transform the chemical energy of the fuel to electricity. The proton exchange membrane (PEM) fuel cells are one of the most common type of fuel cells since they deliver high power density and are lighter and smaller when compared to the other cells. However, commercialization of the PEM fuel cells is challenging due to the high cost of its components. In addition to high catalyst costs, the problem of poor water management is also a vital issue that needs to be overcome. While the gas diffusion layer of a fuel cell is essential for removing the by-product water, the Nafion solution contained in the catalyst layer has hydrophobic properties and is crucial for both preventing the water accumulation and increasing the effectiveness of the fuel cell. In this study, the effects of Carbon:Nafion ratio on the reduction potential was investigated. The cyclic voltammograms (CV) was produced for each ratio, and it was shown that the CVs exhibit characteristics of hydrogen adsorption/desorption peaks. All the linear sweep voltammogram (LSV) curves revealed well distinguished regions of kinetic, mixed and diffusion limited reaction rate. As a result, it was observed that the ratio of 1:5 resulted higher reduction potential compared to 1:3 and 1:7. Finally, a mathematical model was purposed, in which related the rotation rate and platinum coating with the current density, in order to gain insight about the responses of the fuel cell system. The constructed model is tested and validated experimentally for various parameters that are present in the system, and it may be utilized to determine oxygen reaction activities of the catalysts without performing any unnecessary electrochemical tests.     

Parametric analysis of the proton exchange membrane fuel cell performance using design of experiments

Proton exchange membrane fuel cell (PEMFC) performance depends on different fuel cell operating temperatures, humidification temperatures, operating pressures, flow rates, and various combinations of these parameters. This study employed the method of the design of experiments (DOE) to obtain the optimal combination of the six primary operating parameters (fuel cell operating temperatures, operating pressures, anode and cathode humidification temperatures, anode and cathode stoichiometric flow ratios). In the first stage, this study adopted a 2^k−2 fractional factorial design of the DOE to determine whether these factors have significant effects on a response and the interactions between various parameters. Second, the L₂₇(3¹³) orthogonal array of the Taguchi method is utilized to determine the optimal combination of factors for a fuel cell. Based on this study, the operating pressure, the operating temperature, and the interactions between operating temperature and operating pressure have a significant effect on the fuel cell performance. Among them, the operating pressure is the most important contributor. When the operating pressure increases, it should simultaneously lower the effects of other factors. While both the operating temperature and pressure increase simultaneously with that, the other factors are at appropriate conditions, it is possible to improve the fuel cell performance.     

Improvement of the three-dimensional fine-mesh flow field of proton exchange membrane fuel cell (PEMFC) using CFD modeling,artificial neural network and genetic algorithm

This study proposes a systematic methodology for improving PEMFC's performance combining computational fluid dynamic (CFD), artificial neural network (ANN), and intelligent optimization algorithms. Firstly, a three-dimensional (3-D) multiphase PEMFC CFD model with 3-D fine-mesh flow field is developed. Then the key structural features of the fine-mesh flow field are extracted as optimization decision variables, and the sampling points are selected by using the Latin hypercube sampling (LHS) experimental method. The power density and oxygen uniformity index of sampling points are calculated by CFD modeling to form the database, which is used to train the artificial neural network (ANN) surrogate model. Finally, the single-objective optimization (SOO) and multi-objective optimization (MOO) are implemented by using genetic algorithm (GA) and non-dominated sorting genetic algorithm (NSGA-II), respectively. It was found that using trained ANN surrogate models can get a high prediction precision. The maximum power density of SOO is increased by 7.546% than that of base case and is 0.562% larger than that of MOO case. However, the overall pressure drop in cathode flow field of SOO case is greater than that of MOO case and the base case. Furthermore, the oxygen concentration, the oxygen uniformity index and the water removal capacity of MOO case are better than that of SOO case. It is recommended that the improved flow field structure optimized by MOO is more beneficial to improve the overall performance of PEMFC.     

Identifying catalyst layer compositions of proton exchange membrane fuel cells through machine-learning-based approach

Membrane electrode assembly (MEA) is considered a key component of a proton exchange membrane fuel cell (PEMFC). However, developing a new MEA to meet desired properties, such as operation under low-humidity conditions without a humidifier, is a time- and cost-consuming process. This study employs a machine-learning-based approach using K-nearest neighbor (KNN) and neural networks (NN) in the MEA development process by identifying a suitable catalyst layer (CL) recipe in MEA. Minimum redundancy maximum relevance and principal component analysis were implemented to specify the most important predictor and reduce the data dimension. The number of predictors was found to play an essential role in the accuracy of the KNN and NN models although the predictors have self-correlations. The KNN model with a K of 7 was found to minimize the model loss with a loss of 11.9%. The NN model constructed by three corresponding hidden layers with nine, eight, and nine nodes can achieve the lowest error of 0.1293 for the Pt catalyst and 0.031 for PVA as a good additive blending in the CL of the MEA. However, even if the error is low, the prediction of PVA seems to be inaccurate, regardless of the model structure. Therefore, the KNN model is more appropriate for CL recipe prediction.     

Effects of chlorides on the performance of proton exchange membrane fuel cells

This paper investigates the effects of cathode gases containing chloride ions on the proton exchange membrane fuel cell (PEMFC) performance. Chloride solutions are vaporized using an ultrasonic oscillator and mixed with oxygen/air. The salt concentration of the mixed gas in the cathode is set by varying the concentration of the chloride solution. Five-hour tests show that an increase in the concentration of sodium chloride did not significantly affect the cell performance of the PEMFC. It is found that variations in the concentration of chloride do not show significant influence on the cell performance at low current density operating condition. However, for high current density operating conditions and high calcium chloride concentrations, the chloride ion appears to have a considerable effect on cell performance. Experimental results of 108-h tests indicate that the fuel cell operating with air containing calcium chloride has a performance decay rate of 3.446 mV h⁻¹ under the operating condition of current density at 1 A/cm². From the measurements of the I-V polarization curves, it appears that the presence of calcium chloride in the cathode fuel gas affects the cell performance more than sodium chloride does.     

Controlling the microscopic morphology and permeability of catalyst layers in proton exchange membrane fuel cells by adjusting catalyst ink agglomerates

Since agglomerates in catalyst inks affect the catalyst layers (CL) and membrane electrode assemblies (MEA) of proton exchange membrane fuel cell (PEMFC), it is important to study the connection among catalyst agglomerates, CL structure, and MEA performance. This study investigates the effect of Pt/GC catalyst agglomerates on the morphology and permeability of the CL by modulating the properties of the catalyst ink in two different ways. Additionally, MEA was further electrochemically tested to understand the relationship between the catalyst agglomerates and MEA performance. The result shows that High-pressure homogenization is more effective than mechanical shear mixing in dispersing the agglomerates in catalyst inks. However, the excessive homogenization pressure produced larger agglomerated particles, probably because more effective dispersion caused by higher homogenization pressure supplies new chain carriers for polymerization and higher temperature caused by higher homogenization pressure. Moreover, the surface of the CL fabricated in inks prepared by a homogenizer is more uniform, neat, and hydrophilic. But the number of secondary pores in the catalyst layer decreases at excessive homogeneous pressure, and the water permeability becomes poor, which in turn result in lower performance and higher mass transfer resistance. The electrochemical performance test results showed that the MEA with a relatively hydrophobic CL had a performance of 0.707 V at 1000 mA cm⁻², which was 30 mV higher than that with a relatively hydrophilic CL. This study provides insights for better tuning the properties of catalyst ink, CL morphology, and permeability to obtain better performance of MEA.     

Simulation on cathode catalyst layer in proton exchange membrane fuel cell: Sensitivity of design parameters to cell performance and oxygen distribution

The microstructure tuning of the cathode catalyst layer (CCL) is crucial for proton exchange membrane fuel cell (PEMFC) performance. However, a great number of studies have been devoted to the qualitative analysis of CCL design parameters and there is a lack of quantitative studies. In this paper, a cross-dimensional PEMFC agglomerate model is developed to investigate the sensitivities of the CCL design parameters to cell performance and oxygen distribution. Although the results exhibit that the impact of Pt loading on cell performance accounts for 50.7%, the total impact of the Pt radius and I/C ratio (I/C) is as high as 44.9% under the current density of 1000 mA cm^?2. In addition, the variation in I/C directly affects the CCL porosity and thickness of the ionomer on the Pt surface, which determines the oxygen distribution. Typically, under a current density of 1000 mA cm^?2, the impacts of I/C on the average and standard deviation of oxygen concentration account for 42.3% and 51.3%, respectively. The sensitivities of the parameters evolve with the increase in the current density. Pt loading and I/C dominate the cell performance, respectively, with 1200 mA cm^?2 as the demarcation point. This study points out the optimization direction for the design of high-performance CCL.     

Pore network model of the cathode catalyst layer of proton exchange membrane fuel cells: Analysis of water management and electrical performance

A pore network modeling approach is developed to study multiphase transport phenomena inside a porous structure representative of the Cathode Catalyst Layer (CCL) of Proton Exchange Membrane Fuel Cell. A full coupling between two-phase transport, charge transport and heat transport is considered. The liquid water evaporation is also taken into account. The current density profile and the liquid water distribution and production are investigated to understand the liquid production mechanism inside the CCL. The results suggest that the wettability and the pore size distribution have an important impact on the water management inside the cathode catalyst layer and thus on the performances of the proton exchange membrane fuel cell. Simulations show also that Bruggemann correlation used in classical models does not predict correctly gas diffusion.     

Effects of ionomer content and oxygen permeation of the catalyst layer on proton exchange membrane fuel cell cold start-up

We have verified the effectiveness of ionomer as a carrier of oxygen to improve cold start-up of proton exchange membrane fuel cells. Galvanostatic cold start was performed on proton exchange membrane fuel cells to evaluate the effect of ionomer content in the catalyst layer on the durability of power generation at −30 °C. Cell voltage and internal resistance were measured, and polarization analysis was conducted to evaluate the cell voltage reduction. Cold start-up durability improved significantly with higher ionomer content in the catalyst layer because of higher oxygen permeation of ice formed in the catalyst layer. These results enable robust design of membrane electrode assemblies for cold start-up.     

Improving proton exchange membrane fuel cell performance with carbon nanotubes as the material of cathode microporous layer

The cathode microporous layer (MPL) is fabricated by various multiwall carbon nanotubes (CNTs), and its influence on the performance of a proton exchange membrane fuel cell (PEMFC) is evaluated. Three types of CNT with different dimensions are employed in the experiments, and the conventional MPL made by acetylene black (AB) is also considered for the purpose of comparison. The results show that the employment of CNT as MPL composition indeed may improve fuel cell performance significantly in comparison with the case of AB. The type of CNT with the largest tube diameter and straight cylinder in shape exhibits the highest cell performance. The corresponding optimal CNT loading and polytetrafluoroethylene (PTFE) content in the MPL are also evaluated. Results show that the case of cathode MPL composed of 1.5 mg cm^?2 CNT and 20 wt% PTFE exhibits the best performance in all the experimental cases. The present data reveal that the application of CNT for MPL fabrication is beneficial to promote PEMFC performance. Copyright © 2015 John Wiley & Sons, Ltd.     

Carbon film coating on gas diffusion layer for proton exchange membrane fuel cells

This study discusses a novel process to increase the performance of proton exchange membrane fuel cells (PEMFC). In order to improve the electrical conductivity and reduce the surface indentation of the carbon fibers, we modified the carbon fibers with pitch-based carbon materials (mesophase pitch and coal tar pitch). Compared with the gas diffusion backing (GDB), GDB-A240 and GDB-MP have 32% and 33% higher current densities at 0.5 V, respectively. Self-made carbon paper with the addition of a micro-porous layer (MPL) (GDL-A240 and GDL-MP) show improved performance compared with GDB-A240 and GDB-MP. The current densities of GDL-A240 and GDL-MP at 0.5 V increased by 37% and 31% compared with GDL, respectively. This study combines these two effects (carbon film and MPL coating) to promote high current density in a PEMFC.     

Preparation of microporous layer for proton exchange membrane fuel cell by using polyvinylpyrrolidone aqueous solution

A new method of preparing microporous layer (MPL) for proton exchange membrane fuel cell (PEMFC) was presented in this paper. Considering the bad dispersion of PTFE aqueous suspension in the carbon slurry based on ethanol, polyvinylpyrrolidone (PVP) aqueous solution was used to prepare carbon slurry for microporous layer. The prepared gas diffusion layers (GDLs) were characterized by scanning electron microscopy, contact angle system and pore size distribution analyzer. It was found that the GDL prepared with PVP aqueous solution had higher gas permeability, as well as more homogeneous hydrophobicity. Moreover, the prepared GDLs were used in the cathode of fuel cell and evaluated with fuel cell performance and EIS analysis, and the GDL prepared with PVP aqueous solution indicated better fuel cell performance and lower ohmic resistance and mass transfer resistance.